N-cyanoalkyl hexityl amines



N -CYANOALKYL HEXITYL AMINES John D. Zech, Wilmington, Del'., assignor to Atlas Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application October 12, 1953 7 Serial No.' 385,717

10 Claims. Cl. 260-211) advantages will become apparent to those skilled in the art from the following discussionand' disclosure.

The compounds of the present invention may be represented by the following generic formula:

(CeHnOON OnH'ZnCN wherein (C H O represents the hexane pentol residue of a hexityl amine.

n is 1 to 3.

R is selected from the group consisting of hydrogen, alkyl radicals containing 1 to carbon atoms, hydroxy alkyl radicals containing 1 to 10 carbon atoms, aryl radicals, aralkyl radicals, cycloalkyl radicals, and cyanoalkyl radicals containing 1 to 4 carbon atoms. The preferred class of compounds are those wherein R is an alkyl radical. When R is alkyl, those alkyl radicals are preferred containing 1 to 3 carbon atoms. When R is hydroxy alkyl, the hydroxy alkyl radicals are preferred containing 1 to 3 carbon atoms.

The compounds of the present invention are useful as chemical intermediates, particularly for, the synthesis of N-carboxyalkyl hexityl amines as taught in copending application, Serial No. 379,306, filed September 9, 1953, and diamines. These diamines may be readily formed by the catalytic reduction of the cyanoalkyl hexityl amines. A hexityl amine'is an amino derivative of a hexitol such as sorbitol, mannitol, dulcitol, etc., wherein any one of the hydroxy groups has been replaced by an amino group. Such hexityl amines are conveniently prepared by the catalytic reduction of a suitable hexose in the presence of ammonia, primary or secondary amines. For the purpose of the present invention, only primary and secondary hexityl amines are utilized. Suitable such hexityl amines include, but are not limited to, glucamine; N-methyl, N-ethyl, N-propyl, N-octyl, N-octadecyl, N-cetyl, N- hexyl, N-cyclohexyl, N-hydroxyethyl, N-hydroxypropyl, N-dihydroxypropyl, N-benzyl, glucamine; fructamine; N- ethyl, N-propyl, etc. fructamine; etc.

The compounds of the present invention are conveniently prepared by the condensation of a'suitable primary or secondary hexityl amine with a cyanoalkylating agent. A cyanoalkylating agent is one capable of introducing a cyanoalkyl radical into the hexityl amine by reaction with or the removal of an amino hydrogen. Such compounds as hydroxy nitriles, unsaturated nitriles, halogen substituted nitriles, etc. are cyanoalkylating agents. For the purposes of the present invention the term hydroxy nitrile United States Patent nitriles include, but .are not limited to such as: glycolop is meant it cover only those compounds 2,833,757, 'Patented 'May 6, 1958 wherein the by; droxyl group and the nitrile group-are attachedto the same carbon atoms. This is an accepted meaning for the term, but the term is. sometimes .used in arnore I generic sense to cover compounds possessing both a hy-,

droxy group and a nitrile group, regardless of where they are located in the compound. Suitable such hydroxy nitrile, lactonitrile,i a hydroxybutyronitrile. For the pur-" poses of the presentinvention, only those unsaturated nitriles, are acceptable wherein the double bondis com 7 jugated with respect to the nitrile group. Suitable'unsaturated nitriles include, but are not limited to, such as acrylonitrile, methacrylonitrile, crotonom'trile, 'etc.

There are several methods of preparing the compounds of the present method. One method of preparing the" distilled off, preferably'undervacuum. JAn' alternativel and closely allied method, comprises forming thehydroxy nitrile in situ from a suitable aldehyde or ketonej, TIC N and alkali cyanide and then reacting with a suitable hexitylarninein the aforementioned fashion. However, in this latter method a byproduct salt is formed which may be undesirable and difficult to separate'from the N- cyanoalkyl hexityl amine.

A second method of preparing the compounds of the presentinvention comprises reacting a suitable hexityl cyanoalkylating agent such as a halogen substituted nitrile such as chloroacetonitrile, chloropropiononitrile, bromoamine with an unsaturated nitrile as a cyanoalkylating agent. This reaction usually progresses very readily at temperatures ranging from 25 to C. In many cases no catalyst will be required. In other cases, conventional acidic or basic catalysts will improve reaction rates. In many cases it will be convenient to carry out the reaction in the presence of a mutual inert solvent such as methanol, ethanol, pyridine, etc. Solvents are particularly useful in those cases wherein the unsaturated nitrile is immiscible with the hexityl amine used or wherein the hexityl amine has a high melting point, which is above the temperature of the preferred reaction range.

The compounds of the present invention may also be prepared by reacting a suitable hexityl amine. with a propiononitrile, etc. in the presence of an equivalent amount of alkali.

many times desired in view of the incompatibility of the reactants. t

The following examples are given by way of illus tration and are not'intended to limit the scope of, the

present invention in any way.

Example I To a mixture of 195 g. methyl glucamine, 250 cc. of

leaving the product N-methyl N-cyanomethyl glucamine The as a residue. It crystallized slowly on standing. product (236.5 g.) when recrystallized from methanol had a melting point of -96 C. number of 1206.

The preferred temperature range here. is from 50 to C. and for the same reasonsas outlined above, a mutual inert solvent, or diluent, is

It had a hydroxyl V e'To a mixture 0f195 g; methyl glucamine and 300 cc. of

methanol was added 71 g.f'of lactonitrile at 48-59" C. during 12, minutes during \vhich time the methyl gluca= .rninei dissolved. The mixture was heated to reflux (69 C.) and refluxed for 3 hours. ,The solvent was distilled off under vacuum to 93 C. leaving the product (240 g.),

l l methylN-alphacyanoethyl glucamine, as a light yellow resinous-residue 1 ,To a mixture of 195 g. methyl glucamine' and 500 cc. 10f methanol was added 70 cc. of acrylonitrile at 23-46 C. during 100 minutes. The' reaction mixturewas-stirred' wherein R is selected from the group consisting of hydrogen; alkylf'containing 1 to .20 carbon atoms, hydroxyalkyl imam-n 1 m It! carbon atoms aj yl. aralkylrcycloalkyl @dj'cyanoalkylcontaining 1 to 4 carbon atoms; R: is a cyanoalkyl radical containing 1 to 4 carbon atoms;

(Cant s) .represents the hexane pentol residue of a l fltirl a a r r a 2 A compound of the formula:

(CQHlOON wherein R is an alkyl radical containing 1 to 20 carbon atoms; R is a cyanoalkyl, radical containing 1 to 4 carbon atoms; (C H O represents the hexane pentol residue of a hexityl amine.

3. The product .of claim 2 wherein R is an alkyl group containing l to 3 carbon atoms.

4. The product of claim 1 wherein R is an hydroxy alkyl group containing 1 to 3 carbon atoms.

5. A compound of the formula:

(CsH1a 0N CHzCN References Cited in the fileof this patent UNITED STATES PATENTS 2,016,956 Calcott et al. Oct. 8, 1935 2,401,196 Senkus May 28, 1946 2,712,015

Bruson et a1. June 28, 1955 

1. A COMPOUND OF THE FORMULA: 